Playing Reversi with H and N: A copper‐catalyzed intermolecular regioselective hydroamination of styrenes with polymethylhydrosiloxane and hydroxylamine derivatives has been developed. The catalysis accommodates challenging β‐substituted substrates. Moreover, the chiral biphosphine‐ligated copper complex successfully forms benzylamines with good enantiomeric ratios.

A CuCl/(R,R)-Ph-BPE-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with polymethylhydrosiloxane (PMHS) and O-benzoylhydroxylamines has been developed. The efficient and stereoselective net addition of hydrogen and nitrogen atoms provides the corresponding optically active oxa- and azanorbornenyl- and -norbornanylamines in good yields and good enantiomeric ratios.

Scheme 1. Working hypothesis. Bz = benzoyl, L = ligand.

A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl]dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.

An N-heterocyclic carbene (NHC)-catalyzed direct deuteration of aldehydes in a mixed solvent of deuterium oxide (D2O) and cyclopentyl methyl ether was established. The present deuteration is possibly initiated by the formation of a Breslow intermediate from the aldehyde and the NHC, with subsequent trapping by D2O providing the monodeuterated aldehyde.